JPWO2019160029A1 - Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device - Google Patents

Abstract

The present invention provides a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device which are excellent in stability after dissolution and can form a good planar optically anisotropic film. The challenge is to provide. The polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by the following formula (1) and a polymerizable liquid crystal compound represented by the following formula (2). .. L1-SP1-D3-G3-G1-D1-Ar-D2-G2-G4-D4-SP2-L2 ... (1) L1-SP1-D3-A3-A1-D1-Ar-D2-A2-A4 -D4-SP2-L2 ... (2)

Description

The present invention relates to a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device.

A polymerizable compound exhibiting reverse wavelength dispersibility has features such as being able to accurately convert light wavelengths over a wide wavelength range and being able to thin a retardation film due to its high refractive index. Because of this, it is being actively researched.
Further, as a polymerizable compound exhibiting inverse wavelength dispersibility, a T-type molecular design guideline is generally taken, the wavelength of the major axis of the molecule is shortened, and the wavelength of the minor axis located at the center of the molecule is lengthened. Is required to do.
Therefore, it is known that a cycloalkylene skeleton having no absorption wavelength is used for connecting the short-axis skeleton located in the center of the molecule (hereinafter, also referred to as “reverse wavelength dispersion expression part”) and the long-axis of the molecule. (See, for example, Patent Documents 1 to 3).

Japanese Unexamined Patent Publication No. 2010-031223 International Publication No. 2014/010325 Japanese Unexamined Patent Publication No. 2016-081035

As a result of examining the polymerizable compounds exhibiting inverse wavelength dispersibility described in Patent Documents 1 to 3, the present inventors may inferior the stability after dissolution depending on the type of the polymerizable compound, and as a result, It was clarified that it may be difficult to produce an optically anisotropic film having a good surface shape.

Therefore, the present invention presents a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display, which are excellent in stability after dissolution and can form a good planar optically anisotropic film. The subject is to provide the device.

As a result of diligent studies to achieve the above problems, the present inventors have made two types of polymerizable compounds having opposite wavelength dispersibility, in which a part of the ring structure contained in the molecular major axis (side chain) is different. The present invention has been completed by finding that a polymerizable liquid crystal composition in which a liquid crystal compound is used in combination has excellent stability after dissolution and can form a good planar optically anisotropic film.
That is, it was found that the above problem can be achieved by the following configuration.

[1] A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by the formula (1) described later and a polymerizable liquid crystal compound represented by the formula (2) described later.
[2] Described in [1], wherein D ¹ and D ² in the formulas (1) and (2) described later are both −CO—O− *, and * represents the bonding position with Ar. Polymerizable liquid crystal composition.
[3] D ³ and D ⁴ in the formulas (1) and (2) described later are both −CO—O− *, and * represents the bonding position with SP ¹ or SP ² . The polymerizable liquid crystal composition according to 1] or [2].
[4] The polymerizable liquid crystal composition according to any one of [1] to [3], wherein L ¹ and L ² in the formulas (1) and (2) described later both represent polymerizable groups.
[5] The polymerizable liquid crystal according to any one of [1] to [4], wherein one of A ¹ and A ³ in the formula (2) described later represents a cyclohexane ring and the other represents a benzene ring. Composition.
[6] The polymerizable liquid crystal composition according to any one of [1] to [5], wherein A ² and A ⁴ in the formula (2) described later both represent a cyclohexane ring.

[7] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [6].
[8] An optical film having the optically anisotropic film according to [7].
[9] A polarizing plate having the optical film according to [8] and a polarizer.
[10] An image display device having the optical film according to [8] or the polarizing plate according to [9].

According to the present invention, a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate and an image display capable of forming a good planar optically anisotropic film with excellent stability after dissolution. The device can be provided.

FIG. 1A is a schematic cross-sectional view showing an example of the optical film of the present invention. FIG. 1B is a schematic cross-sectional view showing an example of the optical film of the present invention. FIG. 1C is a schematic cross-sectional view showing an example of the optical film of the present invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
Further, in the present specification, the bonding direction of the divalent group (for example, -O-CO-) described is not particularly limited unless the bonding position is specified, and for example, the formula (for example, described later) will be described later. 1) When D ^{1 in} 1) is -CO-O-, assuming that the position bonded to the Ar side is * 1 and the position bonded to the G ¹ side is * 2, D ¹ is * 1-. It may be CO-O- * 2 or * 1-O-CO- * 2.

[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition of the present invention is represented by a polymerizable liquid crystal compound represented by the following formula (1) (hereinafter, also abbreviated as “polymerizable liquid crystal compound (1)”) and a following formula (2). It is a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (hereinafter, also abbreviated as “polymerizable liquid crystal compound (2)”).
L ^1- SP ^1- D ^3- G ^3- G ^1- D ^1- Ar-D ^2- G ^2- G ^4- D ^4- SP ^2- L ² ... (1)
L ^1- SP ^1- D ^3- A ^3- A ^1- D ^1- Ar-D ^2- A ^2- A ^4- D ^4- SP ^2- L ² ... (2)

In the present invention, as described above, the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in which a part of the ring structure contained in the side chain is different is dissolved. It has excellent stability and can form a good planar optically anisotropic film.
This is not clear in detail, but the present inventors speculate as follows.
That is, from the results of Comparative Examples 1 to 3 described later, it can be seen that when the polymerizable liquid crystal compound (1) is blended alone, the stability after dissolution is inferior. It is considered that this is because the polymerizable liquid crystal compound (1) is a compound having a crystal structure having high crystallinity and low solubility by itself.
Therefore, the polymerizable liquid crystal composition in which the polymerizable liquid crystal compound (2) is blended together with the polymerizable liquid crystal compound (1) has similar structures to each other, and when the polymerizable liquid crystal compound (1) is packed. It is considered that the polymerizable liquid crystal compound (2) was mixed there and the packing was hindered, so that the stability after dissolution was improved, and as a result, a good planar optically anisotropic film could be formed.
Hereinafter, each component of the polymerizable liquid crystal composition of the present invention will be described in detail.

[Polymerizable liquid crystal compound (1)]
The polymerizable liquid crystal compound (1) contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound represented by the following formula (1).
L ^1- SP ^1- D ^3- G ^3- G ^1- D ^1- Ar-D ^2- G ^2- G ^4- D ^4- SP ^2- L ² ... (1)

In the above formula (1), G ¹ , G ² , G ³ and G ⁴ each independently represent a cyclohexane ring which may have a substituent.
Further, in the above formula (1), D ¹ , D ² , D ³ and D ⁴ are independently single-bonded or −CO−, −O−, −S−, −C (= S) −. ^{, -CR 1 R 2 -, -} CR 3 = CR 4 -, - NR 5 -, or a divalent linking group formed from these two or more ^thereof, R 1 to R ⁵ are each independently , Hydrogen atom, fluorine atom, or alkyl group having 1 to 4 carbon atoms.
Further, in the above formula (1), SP ¹ and SP ² are independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. Alternatively, a divalent linkage in which one or more of -CH _2- constituting the branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-. Represents a group and Q represents a substituent.
Further, in the above formula (1), L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, Ar is at least one polymerizable group of the formula If (Ar-3) an aromatic ring represented by the, ^{L 1} and ^{L 2} and ^{L 3} and ^{L 4} in formula (Ar-3) Represents.

In the above formula (1), the cyclohexane ring represented by G ¹ , G ² , G ³ and G ⁴ is preferably a trans-1,4-cyclohexylene group.
Further, in the above formula (1), as a substituent that the cyclohexane ring represented by G ¹ , G ² , G ³ and G ⁴ may have, Y ¹ in the formula (Ar-1) described later is present. Examples include the same substituents that may be used.

In the above formula (1), as the divalent linking group represented by D ¹ , D ² , D ³ and D ⁴ , for example, -CO-O-, -C (= S) O-, -CR ¹ R ^{2 -, - CR 1 R 2 -CR} 1 R 2 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 1 R 2 -, - CO-O-CR 1 R 2 -, - O ^{-CO-CR 1 R 2 -,} - CR 1 R 2 -O-CO-CR 1 R 2 -, - CR 1 R 2 -CO-O-CR 1 R 2 -, - NR 5 -CR 1 R 2 - , And −CO-NR ⁵⁻ and the like. R ¹ , R ² and R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

Of these, D ¹ and D ² in the above formula (1) are preferably −CO—O− * because they are easy to synthesize and easily develop liquid crystallinity. Note that * represents the bonding position with Ar.
Further, for the same reason, it is preferable that D ³ and D ⁴ in the above formula (1) are all -O-, -CO-O- *, and -CO-NR ^5- *, and -CO. -O- * is more preferable. Note that * represents the bonding position with SP ¹ or SP ² .

In the above formula (1), examples of the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP ¹ and SP ² include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene. A group, a methylhexylene group, a heptylene group and the like are preferably mentioned. As described above, SP ¹ and SP ² have one or more of -CH _2- constituting a linear or branched alkylene group having 1 to 12 carbon atoms of -O-, -S-, and -NH. It may be a divalent linking group substituted with −, −N (Q) − or −CO−, and the substituent represented by Q is Y in the formula (Ar-1) described later. Examples thereof include the same substituents that ¹ may have.

In the above formula (1), examples of the monovalent organic group represented by L ¹ and L ² include an alkyl group, an aryl group, and a heteroaryl group. The alkyl group may be linear, branched or cyclic, but linear is preferred. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The aryl group may be monocyclic or polycyclic, but monocyclic is preferable. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms. Further, the heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. The heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. Further, the alkyl group, the aryl group and the heteroaryl group may be unsubstituted or have a substituent. Examples of the substituent include the same substituents that Y ¹ in the formula (Ar-1) described later may have.

In the above formula (1), the polymerizable group represented by at least one of L ¹ and L ² is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
As the radically polymerizable group, a generally known radically polymerizable group can be used, and preferred examples thereof include an acryloyl group and a methacryloyl group. In this case, it is known that the acryloyl group is generally faster in terms of polymerization rate, and the acryloyl group is preferable from the viewpoint of improving productivity, but the methacryloyl group can also be used as the polymerizable group in the same manner.
As the cationically polymerizable group, a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and , Vinyloxy group and the like. Of these, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
The following are examples of particularly preferable polymerizable groups.

In the above formula (1), L ¹ and L ² are preferably polymerizable groups, more preferably acryloyl groups or methacryloyl groups, because the film strength after cross-linking is improved.

On the other hand, in the above formula (1), Ar represents any aromatic ring selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-5). In the following formulas (Ar-1) to (Ar-5), * represents the bonding position with D ¹ or D ² in the above formula (1).

Here, in the above formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N (R ⁶ )-, and R ⁶ is. represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y ¹ may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic having 3 to 12 carbon atoms, Represents a ring group.
Specific examples of the alkyl group having 1 to 6 carbon atoms indicated by R ⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl. Examples include a group, an n-pentyl group, and an n-hexyl group.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms indicated by Y ¹ include an aryl group such as a phenyl group, a 2,6-diethylphenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms indicated by Y ¹ include heteroaryl groups such as a thienyl group, a thiazolyl group, a frill group and a pyridyl group.
Examples of the substituent that Y ¹ may have include an alkyl group, an alkoxy group, and a halogen atom.
As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group or an isopropyl group) is preferable. , N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) are more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is used. Is particularly preferable.
As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable, and carbon. It is more preferably an alkoxy group of numbers 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom and a chlorine atom are preferable.

Further, in the above formulas (Ar-1) to (Ar-5), Z ¹ , Z ² and Z ³ are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and carbon. A monovalent alicyclic hydrocarbon group of number 3 to 20, a monovalent aromatic hydrocarbon group of 6 to 20 carbons, a halogen atom, a cyano group, a nitro group, -OR ⁷ , -NR ⁸ R ⁹ , or , -SR ¹⁰ and R ^{7 to} R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring. Good.
As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and specifically, a methyl group and an ethyl group. , Isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group, 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and methyl group, ethyl group, tert-butyl group. Groups are particularly preferred.
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group and an ethylcyclohexyl. Monocyclic saturated hydrocarbon groups such as groups; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodeca Monocyclic unsaturated hydrocarbon groups such as diene; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, Tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Polycyclic saturated hydrocarbon groups such as dodecyl group and adamantyl group; and the like.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and have 6 to 12 carbon atoms. Aryl groups (particularly phenyl groups) are preferred.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
On the other hand, examples of the alkyl group having 1 to 6 carbon atoms represented by R ^{7 to} R ¹⁰ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl. Groups, tert-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned.

Further, in the above formula (Ar-2) and ^{(Ar-3), A} 3 and ^{A 4} are each ^{independently, -O -, - N (R} 11) -, - S-, and from -CO- Represents a group selected from the group, where R ¹¹ represents a hydrogen atom or a substituent.
Examples of the substituent represented by R ¹¹ include the same substituents that Y ¹ in the above formula (Ar-1) may have.

Further, in the above formula (Ar-2), X represents a non-metal atom of Groups 14 to 16 to which a hydrogen atom or a substituent may be bonded.
Examples of the non-metal atoms of Groups 14 to 16 indicated by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent. Specific examples of the substituent include a carbon atom having a substituent. Is, for example, an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, a hydroxyl group, etc. Can be mentioned.

Further, in the above formula (Ar-3), D ⁵ and D ⁶ are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR ^{1 respectively. R 2 -, - CR 3 =} CR 4 -, - NR 5 -, or a divalent linking group formed from these two or more ^thereof, R 1 to R ⁵ are each independently a hydrogen atom, It represents a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
Here, examples of the divalent linking group include the same groups as those described in D ^{1 to} D ⁴ in the above formula (1).

Further, in the above formula (Ar-3), SP ³ and SP ⁴ are independently single-bonded, linear or branched alkylene groups having 1 to 12 carbon atoms, or directly having 1 to 12 carbon atoms. Divalent in which one or more of -CH _2- constituting the chain or branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-. Represents the linking group of, and Q represents the substituent. Examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have.

Further, in the above formula (Ar-3), L ³ and L ⁴ independently represent monovalent organic groups, respectively, and at least 1 of L ³ and L ⁴ and L ¹ and L ^{2 in} the above formula (1). One represents a polymerizable group.
Examples of the monovalent organic group include those similar to those described in L ¹ and L ² in the above formula (1).
In addition, examples of the polymerizable group include those similar to those described in L ¹ and L ² in the above formula (1).

Further, in the above formulas (Ar-4) to (Ar-5), Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and has 2 to 30 carbon atoms. Represents an organic group.
Further, in the above formulas (Ar-4) to (Ar-5), Ay is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and aromatic. It represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of group heterocycles.
Here, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, Q ³ represents a hydrogen atom or may have a substituent alkyl group having 1 to 6 carbon atoms.
Examples of Ax and Ay include those described in paragraphs [0039] to [0995] of Patent Document 2 (International Publication No. 2014/010325).
The alkyl group having 1 to 6 carbon atoms represented by ^{Q 3,} specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert Examples thereof include a-butyl group, an n-pentyl group, an n-hexyl group, and the like, and examples of the substituent include those similar to the substituent that Y ¹ in the above formula (Ar-1) may have. Can be mentioned.

Specific examples of the polymerizable liquid crystal compound represented by the above formula (1) include the following formulas (I-1) to (I-8), (II-n), (III-n) and ( The core (* -Ar- *) represented by any of IV-1) to (IV-5) and the side chain represented by any of the following formulas (M-101) to (M-105) (* -Ar- *). Examples thereof include compounds in which L ^1- SP ^1- D ^3- G ^3- G ^1- D ^1- * or * -D ^2- G ^2- G ^4- D ^4- SP ^2- L ² ) are combined. Among them, the compounds (1-1) to (1-12) shown in Table 1 below are preferably mentioned. In the structure of the core and side chains, * represents the bonding position between the core and the side chains.
In the following description, the following formula (II-n) is referred to as a structure represented by the formula (II-2) when n in the formula is 2. The same applies to the following formula (III-n).

[Polymerizable liquid crystal compound (2)]
The polymerizable liquid crystal compound (2) contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound represented by the following formula (2).
L ^1- SP ^1- D ^3- A ^3- A ^1- D ^1- Ar-D ^2- A ^2- A ^4- D ^4- SP ^2- L ² ... (2)

In the above formula (2), D ¹ , D ² , D ³ and D ⁴ , SP ¹ and SP ² , L ¹ and L ² , and Ar are the same as those described in the above formula (1), respectively. Yes, and the preferred embodiment is the same.
Further, in the above formula (2), A ¹ , A ² , A ³ and A ⁴ may independently have a cyclohexane ring which may have a substituent or a substituent 6 Represents a member unsaturated ring. However, at least one of A ¹ and A ³ represents a 6-membered unsaturated ring which may have a substituent.

In the above formula (2), the cyclohexane rings represented by A ¹ , A ² , A ³ and A ⁴ are the same as those described as G ¹ , G ² , G ³ and G ^{4 in} the above formula (1). ..
Further, in the above formula (2), examples of the 6-membered unsaturated ring represented by A ¹ , A ² , A ³ and A ⁴ include a benzene ring, a cyclohexene ring, and a cyclohexadiene ring.
Further, examples of the substituent that the cyclohexene ring and the 6-membered unsaturated ring may have include the same substituents that Y ¹ in the above-mentioned formula (Ar-1) may have.

In the above formula (2), at least one of A ¹ and A ³ of A ¹ , A ² , A ³ and A ⁴ represents a 6-membered unsaturated ring which may have a substituent, but the reverse is true. from the viewpoint of enhancing the wavelength dispersion, one of a ¹ and a ³ represents a cyclohexane ring is preferable that the other represents a benzene ring, one of a ¹ and a ³ are trans-1,4- More preferably, it represents a silene group and the other represents a 1,4-phenylene group.
Further, from the viewpoint of enhancing the inverse wavelength dispersibility, it is preferable that both A ² and A ⁴ in the above formula (2) represent a cyclohexane ring, and more preferably a trans-1,4-cyclohexylene group. preferable.

Specific examples of the polymerizable liquid crystal compound represented by the above formula (2) include the above-mentioned formulas (I-1) to (I-8), (II-n), (III-n) and. The core (* -Ar- *) represented by any of (IV-1) to (IV-5), the above-mentioned formulas (M-101) to (M-105), and the following formula (M-1-). 1)-(M-1-6), (M-2-1), (M-3-1), (M-4-1), (M-4-2) and (M-5-1) Side chain represented by any of (L ^1- SP ^1- D ^3- A ^3- A ^1- D ^1- * or * -D ^2- A ^2- A ^4- D ^4- SP ^2- L Examples thereof include compounds in which ² ) are combined, and among them, compounds (2-1-1) to (2-12-2) shown in Table 2 below are preferably mentioned. In the structure of the core and side chains, * represents the bonding position between the core and the side chains.
The following formulas (M-1-5), (M-1-6), (M-2-1), (M-3-1), (M-4-1) and (M-4-2) ) Represents a side chain in which the two structures shown below are mixed.

In the present invention, the content of the polymerizable liquid crystal compound (2) is not particularly limited, but is 0.05 to 15% by mass with respect to the total mass of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). Is preferable, and 0.1 to 10% by mass is more preferable for the reason that the durability is good.

[Other polymerizable compounds]
The polymerizable liquid crystal composition of the present invention contains, in addition to the above-mentioned polymerizable liquid crystal compounds (1) and (2), other polymerizable compounds having one or more polymerizable groups, as long as the solubility is not impaired. May be good.
Here, the polymerizable group of the other polymerizable compound is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, it is preferable to have an acryloyl group and a methacryloyl group.

The other polymerizable compound is preferably another polymerizable compound having 1 to 4 polymerizable groups for the reason that the wet heat durability of the optically anisotropic film to be formed is further improved, and is polymerizable. More preferably, it is another polymerizable compound having two groups.

Examples of other polymerizable compounds include the compounds described in paragraphs [0073] to [0074] of JP-A-2016-053709.
In addition, examples of other polymerizable compounds include compounds represented by the formulas (M1), (M2), and (M3) described in paragraphs [0030] to [0033] of JP-A-2014-0770668. More specifically, specific examples described in paragraphs [0046] to [0055] of the same publication can be mentioned.
Further, as the other polymerizable compound, those having the structures of the formulas (1) to (3) described in JP-A-2014-198814 can be preferably used, and more specifically, those having the structures of the same publication [0020 ]-[0035], [0042]-[0050], [0056]-[0057] Specific examples are given.

When such other polymerizable compounds are contained, the content is less than 60% by mass with respect to the total mass including the above-mentioned polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). Is more preferable, and it is more preferably 50% by mass or less, and further preferably 2 to 40% by mass.

[Polymerization initiator]
The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,376,661 and 236,670), acidoin ether (described in US Pat. No. 2,448,828), and α-hydrogen-substituted fragrance. Group acidoine compounds (described in US Pat. No. 2722512), polynuclear quinone compounds (described in US Pat. Nos. 3,043127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US Pat. 35493667 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 421,970), acylphosphine. Oxide compounds (described in Japanese Patent Application Laid-Open No. 63-40799, Japanese Patent Application Laid-Open No. 5-29234, Japanese Patent Application Laid-Open No. 10-95788, Japanese Patent Application Laid-Open No. 10-29997) and the like can be mentioned.
Further, in the present invention, the polymerization initiator is preferably an oxime type polymerization initiator, and specific examples thereof are described in paragraphs [0049] to [0052] of International Publication No. 2017/170443. Agents are mentioned.

〔solvent〕
The polymerizable liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability for forming an optically anisotropic film.
Specific examples of the solvent include ketones (for example, acetone, 2-butanone, methylisobutylketone, cyclohexanone, cyclopentanone, etc.), ethers (for example, dioxane, tetrahydrofuran, etc.), and aliphatic hydrocarbons. (Eg, hexane, etc.), alicyclic hydrocarbons (eg, cyclohexane, etc.), aromatic hydrocarbons (eg, toluene, xylene, trimethylbenzene, etc.), carbon halides (eg, dichloromethane, dichloroethane, dichlorobenzene, etc.) , Chlorotoluene, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (eg, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (eg, methyl cellosolve, ethyl cellosolve, etc.) , Etc.), cellosolve acetates, sulfoxides (eg, dimethylsulfoxide, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.), etc. These may be used alone or in combination of two or more. You may.

[Leveling agent]
The polymerizable liquid crystal composition of the present invention preferably contains a leveling agent from the viewpoint of keeping the surface of the optically anisotropic film smooth and facilitating orientation control.
As such a leveling agent, a fluorine-based leveling agent or a silicon-based leveling agent is preferable because it has a high leveling effect on the amount of addition, and a fluorine-based leveling agent is less likely to cause crying (bloom, bleed). Is more preferable.
Specific examples of the leveling agent include the compounds described in paragraphs [0079] to [0102] of JP-A-2007-069471, and the general formulas described in JP-A-2013-047204. The compound represented by I) (particularly the compound described in paragraphs [0020] to [0032]) and the compound represented by the general formula (I) described in JP2012-211306 (particularly [0022]). -[0029] paragraphs), liquid crystal orientation promoters represented by the general formula (I) described in JP-A-2002-129162 (particularly [0076] to [0078] and [0082]- Compounds described in paragraph [0084], compounds represented by general formulas (I), (II) and (III) described in JP-A-2005-09248 (particularly paragraphs [0092] to [0996]). The compounds described in (1) and the like. In addition, it may also have a function as an orientation control agent described later.

[Orientation control agent]
The polymerizable liquid crystal composition of the present invention may contain an orientation control agent, if necessary.
The orientation control agent can form various orientation states such as homeotropic orientation (vertical orientation), tilt orientation, hybrid orientation, and cholesteric orientation in addition to homogenius orientation, and can make a specific orientation state more uniform and more uniform. It can be realized by precise control.

As the orientation control agent that promotes homogenous orientation, for example, a low molecular weight orientation control agent or a high molecular weight orientation control agent can be used.
Examples of the low molecular weight orientation control agent include paragraphs [0009] to [0083] of JP-A-2002-20363, paragraphs [0111]-[0120] of JP-A-2006-106662, and JP-A-2012. The description in paragraphs [0021] to [0029] of JP-A-21306 can be taken into consideration, and this content is incorporated in the present specification.
Further, as the polymer orientation control agent, for example, paragraphs [0021] to [0057] of JP-A-2004-198511 and paragraphs [0121] to [0167] of JP-A-2006-106662 are referred to. And this content is incorporated herein by reference.

Examples of the orientation control agent for forming or promoting homeotropic orientation include boronic acid compounds and onium salt compounds. Specifically, paragraphs [0023] to [0032] of JP-A-2008-225281. , Paragraphs [0052] to [0058] of JP2012-208397A, paragraphs [0024] to [0055] of JP2008-026730, and [0043] to [0055] of JP2016-193869. The compounds described in paragraphs and the like can be taken into account, the contents of which are incorporated herein by reference.

On the other hand, the cholesteric orientation can be realized by adding a chiral agent to the polymerizable composition of the present invention, and the turning direction of the cholesteric orientation can be controlled by the direction of the chiral property. The pitch of the cholesteric orientation can be controlled according to the orientation regulating force of the chiral agent.

When the orientation control agent is contained, the content thereof is preferably 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total solid content mass in the polymerizable liquid crystal composition. More preferred. When the content is in this range, it is possible to obtain a uniform and highly transparent optically anisotropic film without precipitation, phase separation, orientation defects, etc., while achieving the desired orientation state.
These orientation control agents can further impart a polymerizable functional group, particularly a polymerizable functional group that can be polymerized with the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition of the present invention.

[Other ingredients]
The polymerizable liquid crystal composition of the present invention may contain a component other than the above-mentioned components, for example, a liquid crystal compound other than the above-mentioned polymerizable liquid crystal compound, a surfactant, a tilt angle control agent, an orientation aid, and a plasticizer. Examples thereof include agents and cross-linking agents.

[Optical anisotropic film]
The optically anisotropic film of the present invention is an optically anisotropic film obtained by polymerizing the above-mentioned polymerizable liquid crystal composition of the present invention.
Examples of the method for forming the optically anisotropic film include a method in which the above-mentioned polymerizable liquid crystal composition of the present invention is used to obtain a desired orientation state and then immobilized by polymerization.
Here, the polymerization conditions are not particularly limited, but it is preferable to use ultraviolet rays in the polymerization by light irradiation. Irradiation amount ^is preferably ^{10mJ / cm 2 ~50J / cm 2} , more preferably ^{20mJ / cm 2 ~5J / cm 2} , more preferably 30mJ ^/ cm ² ~3J ^/ cm 2 , 50 to 1000 mJ / cm ² is particularly preferable. Further, in order to promote the polymerization reaction, it may be carried out under heating conditions.
In the present invention, the optically anisotropic film can be formed on an arbitrary support in the optical film of the present invention described later or on a polarizer in the polarizing plate of the present invention described later.

The optically anisotropic film of the present invention preferably satisfies the following formula (3).
0.50 <Re (450) / Re (550) <1.00 ... (3)
Here, in the above formula (3), Re (450) represents the in-plane lettering of the optically anisotropic film at a wavelength of 450 nm, and Re (550) represents the in-plane letter of the optically anisotropic film at a wavelength of 550 nm. Represents the optics. If the measurement wavelength of the retardation is not specified in the present specification, the measurement wavelength is 550 nm.
The values of in-plane retardation and retardation in the thickness direction are values measured using light of a measurement wavelength using AxoScan OPMF-1 (manufactured by Optoscience).
Specifically, by inputting the average refractive index ((Nx + Ny + Nz) / 3) and film thickness (d (μm)) in AxoScan OPMF-1.
Slow phase axial direction (°)
Re (λ) = R0 (λ)
Rth (λ) = ((nx + ny) /2-nz) × d
Is calculated.
Although R0 (λ) is displayed as a numerical value calculated by AxoScan OPMF-1, it means Re (λ).

The optically anisotropic film of the present invention is preferably a positive A plate or a positive C plate, and more preferably a positive A plate.

Here, the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.
The refractive index in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized) is nx, the refractive index in the direction orthogonal to the slow phase axis in the plane in the plane is ny, and the refraction in the thickness direction. When the rate is nz, the positive A plate satisfies the relation of the formula (A1), and the positive C plate satisfies the relation of the formula (C1). The positive A plate shows a positive value for Rth, and the positive C plate shows a negative value for Rth.
Equation (A1) nx> ny≈nz
Equation (C1) nz> nx≈ny
The above "≈" includes not only the case where both are completely the same, but also the case where both are substantially the same.
“Substantially the same” means that in a positive A plate, for example, (ny-nz) × d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. It is included in "ny≈nz", and when (nx-nz) xd is -10 to 10 nm, preferably -5 to 5 nm, it is also included in "nx≈nz". Further, in the positive C plate, for example, when (nx−ny) × d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, it is also included in “nx≈ny”.

When the optically anisotropic film of the present invention is a positive A plate, Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, from the viewpoint of functioning as a λ / 4 plate. It is more preferably 130 to 150 nm, and particularly preferably 130 to 140 nm.
Here, the "λ / 4 plate" is a plate having a λ / 4 function, and specifically, a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light). It is a plate having.

[Optical film]
The optical film of the present invention is an optical film having the optically anisotropic film of the present invention.
1A, 1B and 1C (hereinafter, these drawings are abbreviated as "FIG. 1" when no particular distinction is required) are schematic cross-sectional views showing an example of the optical film of the present invention, respectively.
Note that FIG. 1 is a schematic view, and the thickness relationship and positional relationship of each layer do not always match the actual ones, and the support, alignment film, and hard coat layer shown in FIG. 1 all have an arbitrary configuration. It is a member.
The optical film 10 shown in FIG. 1 has a support 16, an alignment film 14, and an optically anisotropic film 12 in this order.
Further, as shown in FIG. 1B, the optical film 10 may have a hard coat layer 18 on the side opposite to the side where the alignment film 14 of the support 16 is provided, and as shown in FIG. 1C, the optical film 10 may have a hard coat layer 18. The hard coat layer 18 may be provided on the side of the optically anisotropic film 12 opposite to the side on which the alignment film 14 is provided.
Hereinafter, various members used in the optical film of the present invention will be described in detail.

[Optically anisotropic film]
The optically anisotropic film of the optical film of the present invention is the above-mentioned optically anisotropic film of the present invention.
In the optical film of the present invention, the thickness of the optically anisotropic film is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

[Support]
As described above, the optical film of the present invention may have a support as a base material for forming an optically anisotropic film.
Such a support is preferably transparent, and specifically, the light transmittance is preferably 80% or more.

Examples of such a support include a glass substrate and a polymer film, and examples of the polymer film material include a cellulose-based polymer; an acrylic-based polymer having an acrylic acid ester polymer such as polymethylmethacrylate and a lactone ring-containing polymer. Polymers; Thermoplastic norbornene-based polymers; Polycarbonate-based polymers; Polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; Stylized polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin); Polyethylene, polypropylene, ethylene and propylene Polyolefin-based polymers such as polymers; Vinyl chloride-based polymers; Amido-based polymers such as nylon and aromatic polyamides; Imid-based polymers; Sulfon-based polymers; Polyether sulfone-based polymers; Polyether ether ketone-based polymers; Polyphenylene sulfide-based polymers Examples thereof include vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers; allylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; or polymers obtained by mixing these polymers.
Further, the polarizer described later may also serve as such a support.

In the present invention, the thickness of the support is not particularly limited, but is preferably 5 to 60 μm, and more preferably 5 to 30 μm.

[Alignment film]
When the optical film of the present invention has any of the above-mentioned supports, it is preferable that the optical film has an alignment film between the support and the optically anisotropic film. The support described above may also serve as an alignment film.

The alignment film generally contains a polymer as a main component. The polymer material for an alignment film has been described in a large number of documents, and a large number of commercially available products are available.
The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, or a derivative thereof. Particularly modified or unmodified polyvinyl alcohol is preferable.
Regarding the alignment film that can be used in the present invention, for example, the alignment film described in International Publication No. 01/88574, p. 43, line 24 to p. 49, line 8; paragraphs [0071] to [0995] of Japanese Patent No. 3907735. ], And the like; a liquid crystal alignment film formed by the liquid crystal alignment agent described in Japanese Patent Application Laid-Open No. 2012-155308; and the like.

In the present invention, it is also preferable to use a photoalignment film as the alignment film because it is possible to prevent surface deterioration by not contacting the surface of the alignment film when the alignment film is formed.
The photoalignment film is not particularly limited, but is a polymer material such as a polyamide compound or a polyimide compound described in paragraphs [0024] to [0043] of International Publication No. 2005/096041; described in JP2012-155308A. A liquid crystal alignment film formed by a liquid crystal alignment agent having a photo-oriented group; a trade name LPP-JP265CP manufactured by Polyimide, Inc. can be used.

Further, in the present invention, the thickness of the alignment film is not particularly limited, but from the viewpoint of alleviating the surface irregularities that may exist on the support and forming an optically anisotropic film having a uniform film thickness, 0. It is preferably 01 to 10 μm, more preferably 0.01 to 1 μm, and even more preferably 0.01 to 0.5 μm.

[Hard coat layer]
The optical film of the present invention preferably has a hard coat layer in order to impart physical strength to the film. Specifically, the hard coat layer may be provided on the side opposite to the side where the alignment film of the support is provided (see FIG. 1B), and the side where the alignment film of the optically anisotropic film is provided. May have a hard coat layer on the opposite side (see FIG. 1C).
As the hard coat layer, those described in paragraphs [0190] to [0196] of JP2009-98658A can be used.

[Other optically anisotropic films]
The optical film of the present invention may have another optically anisotropic film in addition to the optically anisotropic film of the present invention.
That is, the optical film of the present invention may have a laminated structure of the optically anisotropic film of the present invention and another optically anisotropic film.
Such other optically anisotropic films do not contain either or both of the above-mentioned polymerizable liquid crystal compound (1) and the above-mentioned polymerizable liquid crystal compound (2), and the above-mentioned other polymerizable compounds (particularly, particularly). It is not particularly limited as long as it is an optically anisotropic film obtained by using a liquid crystal compound).
Here, in general, liquid crystal compounds can be classified into rod-shaped type and disk-shaped type according to their shapes. Furthermore, there are low molecular weight and high molecular weight types, respectively. A polymer generally refers to a polymer having a degree of polymerization of 100 or more (polymer physics / phase transition dynamics, by Masao Doi, p. 2, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but it is preferable to use a rod-shaped liquid crystal compound or a discotic liquid crystal compound (disk-shaped liquid crystal compound). Two or more kinds of rod-shaped liquid crystal compounds, two or more kinds of disk-shaped liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound may be used. For the immobilization of the above-mentioned liquid crystal compound, it is more preferable to form a rod-shaped liquid crystal compound or a disk-shaped liquid crystal compound having a polymerizable group, and the liquid crystal compound may have two or more polymerizable groups in one molecule. More preferred. When the liquid crystal compound is a mixture of two or more kinds, it is preferable that at least one kind of liquid crystal compound has two or more polymerizable groups in one molecule.
As the rod-shaped liquid crystal compound, for example, those described in claim 1 of JP-A No. 11-513019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used, and discotics can be used. As the liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038 can be preferably used. However, it is not limited to these.

[UV absorber]
The optical film of the present invention preferably contains an ultraviolet (UV) absorber in consideration of the influence of external light (particularly ultraviolet rays).
The ultraviolet absorber may be contained in the optically anisotropic film of the present invention, or may be contained in a member other than the optically anisotropic film constituting the optical film of the present invention. As the member other than the optically anisotropic film, for example, a support is preferably mentioned.
As the ultraviolet absorber, any conventionally known one capable of exhibiting ultraviolet absorption can be used. Among such ultraviolet absorbers, a benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorber may be used from the viewpoint of obtaining the ultraviolet absorbing ability (ultraviolet blocking ability) used in an image display device because of its high ultraviolet absorbing ability. preferable.
Further, in order to widen the absorption range of ultraviolet rays, two or more kinds of ultraviolet absorbers having different maximum absorption wavelengths can be used in combination.
Specific examples of the ultraviolet absorber include the compounds described in paragraphs [0258] to [0259] of JP2012-18395, paragraphs [0055] to [0105] of JP2007-72163. Examples thereof include the compounds described in.
Further, as commercially available products, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, Tinuvin 1577 (all manufactured by BASF) and the like can be used.

[Polarizer]
The polarizing plate of the present invention has the above-mentioned optical film of the present invention and a polarizer.
Further, the polarizing plate of the present invention can be used as a circular polarizing plate when the above-mentioned optically anisotropic film of the present invention is a λ / 4 plate (positive A plate).
Further, when the optically anisotropic film of the present invention described above is a λ / 4 plate (positive A plate), the polarizing plate of the present invention has a slow phase axis of the λ / 4 plate and an absorption axis of a polarizer described later. The angle formed by the light is preferably 30 to 60 °, more preferably 40 to 50 °, further preferably 42 to 48 °, and particularly preferably 45 °.
Here, the "slow phase axis" of the λ / 4 plate means the direction in which the refractive index becomes maximum in the plane of the λ / 4 plate, and the "absorption axis" of the polarizer means the direction in which the absorbance is highest. To do.

[Polarizer]
The polarizer of the polarizing plate of the present invention is not particularly limited as long as it is a member having a function of converting light into specific linearly polarized light, and conventionally known absorption-type polarizing elements and reflection-type polarization elements can be used. ..
As the absorption type polarizer, an iodine-based polarizer, a dye-based polarizer using a dichroic dye, a polyene-based polarizer, and the like are used. Polarized light produced by adsorbing iodine or a dichroic dye on polyvinyl alcohol and stretching it can be applied to both iodine-based polarized light and dye-based polarized light. Children are preferred.
Further, as a method for obtaining a polarizer by stretching and dyeing a laminated film having a polyvinyl alcohol layer formed on a substrate, Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 46910205, and Japanese Patent No. No. 4751481 and No. 4751486 can be mentioned, and known techniques for these polarizers can also be preferably used.
As the reflective polarizer, a polarizer in which thin films having different birefringence are laminated, a wire grid type polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wave plate are combined, and the like are used.
Among them, a polymer containing a polyvinyl alcohol-based resin (-CH _2- CHOH- as a repeating unit. In particular, at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers, in that the adhesion is more excellent. It is preferable that the polymer contains one).

In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 μm to 60 μm, more preferably 5 μm to 30 μm, and even more preferably 5 μm to 15 μm.

[Adhesive layer]
In the polarizing plate of the present invention, an adhesive layer may be arranged between the optically anisotropic film in the optical film of the present invention and the polarizer.
The pressure-sensitive adhesive layer used for laminating the optically anisotropic film and the polarizer includes, for example, the ratio of the storage elastic modulus G'measured by a dynamic viscoelasticity measuring device to the loss elastic modulus G'(tan δ =). G "/ G') represents a substance having a value of 0.001 to 1.5, and includes so-called adhesives, substances that easily creep, and the like. Examples of the pressure-sensitive adhesive that can be used in the present invention include, but are not limited to, a polyvinyl alcohol-based pressure-sensitive adhesive.

[Image display device]
The image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention.
The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, and a plasma display panel.
Of these, a liquid crystal cell and an organic EL display panel are preferable, and a liquid crystal cell is more preferable. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element, and the liquid crystal display device is preferable. More preferred.

[Liquid crystal display device]
The liquid crystal display device which is an example of the image display device of the present invention is a liquid crystal display device having the above-mentioned polarizing plate of the present invention and a liquid crystal cell.
In the present invention, among the polarizing plates provided on both sides of the liquid crystal cell, it is preferable to use the polarizing plate of the present invention as the polarizing plate on the front side, and the polarizing plate of the present invention as the polarizing plate on the front side and the rear side. Is more preferable to use.
The liquid crystal cells constituting the liquid crystal display device will be described in detail below.

<LCD cell>
The liquid crystal cell used in the liquid crystal display device is preferably a VA (Vertical Element) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. It is not limited to.
In the TN mode liquid crystal cell, the rod-shaped liquid crystal molecules are substantially horizontally oriented when no voltage is applied, and are further twisted to 60 to 120 °. The TN mode liquid crystal cell is most often used as a color TFT liquid crystal display device, and has been described in many documents.
In the VA mode liquid crystal cell, the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied. In the VA mode liquid crystal cell, (1) a VA mode liquid crystal cell in a narrow sense in which rod-shaped liquid crystal molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. 2-). In addition to (described in Japanese Patent Application Laid-Open No. 176625), (2) a liquid crystal cell (SID97, Digital of technique. Papers (Proceedings) 28 (1997) 845 in which the VA mode is multi-domainized for expanding the viewing angle). ), (3) Liquid crystal cells in a mode (n-ASM mode) in which rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted and multi-domain oriented when a voltage is applied (Proceedings of the Japan Liquid Crystal Discussion Group 58-59). (1998)) and (4) SURVIVAL mode liquid crystal cells (announced at LCD International 98) are included. Further, it may be any of PVA (Patternized Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Sustained Alignment). Details of these modes are described in Japanese Patent Application Laid-Open No. 2006-215326 and Japanese Patent Application Laid-Open No. 2008-538819.
In the liquid crystal cell in the IPS mode, the rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond in a plane by applying an electric field parallel to the substrate surface. In the IPS mode, the display is black when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other. Methods for reducing leakage light during black display in an oblique direction and improving the viewing angle by using an optical compensation sheet are described in JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522. It is disclosed in JP-A-11-133408, JP-A-11-305217, JP-A-10-307291, and the like.

[Organic EL display device]
Examples of the organic EL display device which is an example of the image display device of the present invention include, from the visual side, a polarizer, a λ / 4 plate (positive A plate) made of the optically anisotropic film of the present invention, and an organic EL. A mode having a display panel in this order is preferably mentioned.
Further, the organic EL display panel is a display panel configured by using an organic EL element having an organic light emitting layer (organic electroluminescence layer) sandwiched between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

<Synthesis of compound (I-1)>
The synthesis of the compound (I-1) represented by the following formula (I-1) was carried out with reference to the method described in Justus Liebigs Annalen der Chemie, 726,103-109 (1969).

<Synthesis of compound (I-4)>
The compound (I-4) represented by the following formula (I-4) was synthesized by the same method as that of the compound (I-1) except that benzoquinone was changed to 2-t-butylbenzoquinone.

<Synthesis of compound (S-1-c)>

As shown in the above scheme, 125 g (0.462 mol) of dimethyl 4,4-biphenyldicarboxylic acid (S-1-a) was added to 1000 mL of acetic acid, and 12.5 g of a palladium carbon catalyst (wet product) was added. A catalytic hydrogenation reaction was carried out in an autoclave at 130 ° C. and 2 MPa.
After completion of the reaction, the catalyst was removed by filtration after cooling to room temperature (23 ° C.).
Then, acetic acid was distilled off under reduced pressure, and then ethyl acetate and an aqueous sodium hydrogen carbonate solution were added. Then, the mixture was stirred and separated to remove the aqueous layer, and the organic layer was further washed with 10% saline. Sodium sulfate was added to this solution, dried, and the solvent was concentrated to obtain dimethyl 4,4′-dicyclohexanedicarboxylic acid (S-1-b) (130 g).
No further purification was carried out, followed by dimethyl 4,4'-dicyclohexanedicarboxylic acid (130 g), potassium hydroxide pellets (made by Aldrich, 90% purity) 86.3 g, cumene 1300 mL, and polyethylene glycol 2000 (Tokyo). (Manufactured by Kasei Kogyo Co., Ltd.) 10 mL was mixed, a Dean Stark tube was attached, and the mixture was heated and stirred at 120 ° C. After distilling off the methanol, the temperature was set to 180 ° C., and the mixture was heated under reflux for 20 hours while distilling off the solvent. The reaction progress was confirmed by NMR (Nuclear Magnetic Resonance), and after the reaction was completed, the mixture was cooled, 1300 mL of ethanol was added to the reaction solution, and the precipitated potassium salt was collected by filtration.
Next, this potassium salt was dissolved in 1300 ml of water, concentrated hydrochloric acid was added under ice-cooling until the pH of the system became 3, and the precipitated carboxylic acid was collected by filtration to recover the crude product.
The recovered crude material was suspended in 500 mL of acetone, stirred at 50 ° C. for 30 minutes, cooled to room temperature, collected by filtration, and 93.9 g (yield 80) of dicyclohexanedicarboxylic acid (S-1-c) crystals was obtained. %)Obtained.

As shown in the scheme above, 10.0 g (39.3 mmol) of compound (S-1-c), 50 mL of N, N-dimethylacetamide (DMAc), 8.0 ml (78.6 mmol) of triethylamine, and 2,6. 433 mg of -di-t-butyl-4-methylphenol was mixed at room temperature (23 ° C.).
To the mixture was added 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 30 ml of 1N hydrochloric acid water and 50 ml of toluene were added, and the mixture was stirred at 40 ° C. and then separated. The organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution, 1% aqueous sodium hydrogen carbonate solution and 1% aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off under reduced pressure. After adding 40 mL of hexane to the residue to precipitate crystals, the mixture was cooled to 5 ° C., stirred under ice water for 30 minutes, and then the crude material was collected by filtration. The obtained crude product was turbid in 40 mL of hexane, stirred for 30 minutes, collected by filtration, and air-dried to obtain 5.39 g of compound (S-1-d) (yield 36%). ..

[Synthesis of polymerizable liquid crystal compound (1-1)]

As shown in the above scheme, 12.90 g (33.9 mmol) of compound (S-1-d), 40 mL of toluene, 2.82 g of N, N-dimethylformamide (DMF), and 2,6-di-t-. 15 mg of butyl-4-methylphenol was mixed at room temperature, and the internal temperature was cooled to 5 ° C. 3.94 g (33.1 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise to the mixture so that the internal temperature did not rise above 10 ° C. After stirring at 20 ° C. for 30 minutes, the separated lower layer was removed. The internal temperature was cooled to 5 ° C., and a solution of 3.83 g (15.4 mmol) of compound (I-1) in tetrahydrofuran (THF) (100 ml) was added. After adding 8.57 g (66.3 mmol) of N, N-diisopropylethylamine (DIPEA) so that the internal temperature did not rise above 10 ° C., the mixture was stirred at room temperature for 2 hours. After stirring, 100 mL of isopropyl alcohol and 50 mL of water were added dropwise in this order to stop the reaction, and the precipitated crystals were separated into furnaces. The obtained crude product was dissolved in 90 mL of THF and then recrystallized by adding 200 mL of isopropyl alcohol to obtain 13.5 g (13.9 mmol) of the polymerizable liquid crystal compound (1-1) (yield 90%). ..

[Synthesis of polymerizable liquid crystal compound (1-3)]

As shown in the above scheme, 2.53 g (6.65 mmol) of compound (S-1-d), 8 mL of toluene, 0.5 mL of N, N-dimethylformamide (DMF), 2,6-di-t-butyl- 33 mg of 4-methylphenol was mixed at room temperature, and the internal temperature was cooled to 5 ° C. To the mixture, 0.58 ml (7.98 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise so that the internal temperature did not rise above 10 ° C. After stirring at 20 ° C. for 30 minutes, the separated lower layer was removed. The internal temperature was cooled to 5 ° C., and a solution (10 ml) of 0.92 g (3.02 mmol) of compound (I-4) in tetrahydrofuran (THF) was added. 2.90 ml (16.6 mmol) of N, N-diisopropylethylamine (DIPEA) was added dropwise so that the internal temperature did not rise above 10 ° C., and then the mixture was stirred at 30 ° C. for 2 hours. After stirring, 15 ml of 1N hydrochloric acid water and 15 ml of ethyl acetate were added to stop the reaction, and the liquid was separated. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was concentrated by distillation under reduced pressure. 30 mL of isopropyl alcohol was added dropwise to the obtained concentrated solution at an internal temperature of 40 ° C., and then the mixture was cooled to an internal temperature of 5 ° C. to precipitate crystals and separated by filtration. The obtained crude product was dissolved in 10 mL of ethyl acetate and then recrystallized by adding 35 mL of isopropyl alcohol to obtain 2.65 g (2.58 mmol) of the polymerizable liquid crystal compound (I-3) (yield). 85%).

[Synthesis of polymerizable liquid crystal compound (1-9)]
A polymerizable liquid crystal compound (1-9) represented by the following formula was synthesized according to the method described in paragraphs [0161] to [0163] of JP-A-2010-084032.

<Synthesis of compound (S-2-c)>

As shown in the above scheme, a suspension of 60.0 g of aluminum chloride and 30.0 g of acetyl chloride in 120 mL of carbon disulfide was cooled to −50 ° C., and 30.0 g of cyclohexene was added dropwise. After stirring at −20 ° C. or lower for 15 minutes, the solution portion was removed, 300 mL of benzene was added, and the mixture was stirred at 45 ° C. for 3 hours. The reaction mixture was ice-cooled, the reaction was stopped with 100 mL of 1N hydrochloric acid, and the organic layer was washed with 1N hydrochloric acid and a 10% NaOH aqueous solution. The reaction mixture was dried over magnesium sulfate and then purified by silica gel column chromatography to obtain 32.0 g of compound (S-2-a).
17.3 g of aluminum chloride and 100 mL of dichloroethane were cooled to 5-10 ° C., and 12.9 g of compound (S-2-a) was added. 5.1 g of acetyl chloride was added dropwise at 5-10 ° C, and the mixture was stirred at 5-10 ° C for 1 hour. 100 mL of water was added, the reaction was stopped, and the organic layer was dried over magnesium sulfate. Purification by silica gel column chromatography gave 9.3 g (yield 60%) of compound (S-2-b).
After adding 0.28 g of tetrabutylammonium chloride and 2.8 g of sodium sulfate to a solution of 75.0 g of sodium hypochlorite and 13.9 g of sodium hydroxide, 8.6 g of compound (S-2-b) was added. , 60 ° C. for 3 hours. After cooling to room temperature, the pH was adjusted to 2 with 30% sulfuric acid, and the precipitated carboxylic acid was collected by filtration to recover the crude product. The recovered crude material was suspended in 50 mL of acetone, stirred at 50 ° C. for 30 minutes, cooled to room temperature, and collected by filtration to obtain 7.8 g (yield 90%) of compound (S-2-c).

<Synthesis of compound (S-2-d)>

Then, as shown in the above scheme, 5.0 g (20 mmol) of compound (S-2-c), 50 mL of N, N-dimethylacetamide (DMAc), 5.6 ml (40 mmol) of triethylamine, and 2,6-di. 43 mg of -t-butyl-4-methylphenol was mixed at room temperature. To the mixture was added 4.9 g (22 mmol) of 4-methylsulfonyloxybutyl acrylate and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 12.5 ml of 1N hydrochloric acid water and 25 ml of toluene were added, and the mixture was stirred at 40 ° C. and then separated. The organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution, 1% aqueous sodium hydrogen carbonate solution and 1% aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography gave 2.6 g of compound (S-2-d) (yield 35%).

[Synthesis of polymerizable liquid crystal compound (2-1-7)]

Compound (S-2-d) 1.0 g (2.7 mmol), ethyl acetate (EA) 10 mL, N, N-dimethylacetamide (DMAc) 3 mL, 2,6-di-t-butyl-4-methylphenol 5 mg Was mixed at room temperature, and the internal temperature was cooled to 5 ° C. 0.24 mL (3.2 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise to the mixture so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C. for 1 hour, 0.30 g (1.2 mmol) of compound (I-1) in tetrahydrofuran (THF) (5 ml) was added. After adding 0.94 ml (5.4 mmol) of N, N-diisopropylethylamine (DIPEA), the mixture was stirred at room temperature for 6 hours. After stirring, 10 ml of 1N hydrochloric acid water and 10 ml of ethyl acetate were added to stop the reaction, and the liquid was separated. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 1.0 g (1.1 mmol) of a polymerizable liquid crystal compound (2-1-7) (yield 88%).

<Synthesis of compound (S-1-e)>

Compound (S-1-d) 30.0 g (79 mmol), compound (I-1) 39.2 g (158 mmol), tetrahydrofuran 525 mL, chloroform 175 mL, 2,6-di-t-butyl-4-methylphenol 0. 44 g was mixed at room temperature and 22.7 g (119 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added. 1.44 g of dimethylaminopyridine was added, and the mixture was stirred at room temperature for 3 hours. 220 ml of 1N hydrochloric acid water and 220 ml of ethyl acetate were added to stop the reaction, and the liquid was separated. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography to obtain 25.0 g (41 mmol) of compound (S-1-e) (yield 52%).

[Synthesis of polymerizable liquid crystal compound (2-1-5)]

Compound (S-1-e) 1.63 g (2.7 mmol), compound (S-2-d) 1.0 g (2.7 mmol), tetrahydrofuran 20 mL, chloroform 6 mL, 2,6-di-t-butyl- 15 mg of 4-methylphenol was mixed at room temperature and 0.61 g (3.2 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added. 0.05 g of dimethylaminopyridine was added, and the mixture was stirred at room temperature for 3 hours. 10 ml of 1N hydrochloric acid water and 10 ml of ethyl acetate were added to stop the reaction, and the liquid was separated. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography to obtain 2.2 g (2.3 mmol) of the polymerizable liquid crystal compound (2-1-5) (yield 85%).

[Synthesis of polymerizable liquid crystal compound (2-3-1)]
The following formula is used in the same manner as the polymerizable liquid crystal compound (2-1-5) except that the compound (I-1) used for the synthesis of the compound (S-1-e) is replaced with the compound (I-4). A polymerizable liquid crystal compound (2-3-1) represented by is synthesized.

[Synthesis of polymerizable liquid crystal compound (2-9-2)]
In the same manner as the polymerizable liquid crystal compound (2-1-7), except that the compound I described in paragraph [0161] of JP2010-084032A was used instead of the compound (I-1). A polymerizable liquid crystal compound (2-9-2) represented by the following formula was synthesized.

[Solubility]
The solubility of the synthesized polymerizable liquid crystal compound was measured by the method shown below. The results are shown in Tables 3 and 4 below. In the evaluation of the solubility of Examples 1 to 8 in 3 and Table 4 below, the polymerizable liquid crystal compounds shown in Tables 3 and 4 below were mixed at the ratios shown in Tables 3 and 4 below. Evaluated with a mixture.
First, 1.0 g of the polymerizable liquid crystal compound was weighed in a 10 mL sample bottle in total, and 1.5 g of the solvent was added until the solid content became 40% by mass. Then, it was shaken well by hand at 50 ° C., left at room temperature (23 ° C.) for 10 minutes, and then visually observed, and if it was clear, the process was completed, and the solubility was determined to be 40% by mass.
On the other hand, if there was any undissolved residue, a solvent was added so that the solid content was 35% by mass (+0.36 g). Then, it was shaken well by hand at 50 ° C., left at room temperature (23 ° C.) for 10 minutes, and then visually observed, and if it was clear, it was terminated, and it was determined to be 35% by mass.
Further, if there was any undissolved residue, a solvent was added so as to be 30% by mass. The same operation was repeated in increments of 5% by mass until it reached 5% by mass. If there was any undissolved residue, it was determined that the solubility was less than 5% by mass (<5% by mass), and the process was completed. CPN (cyclopentanone) was used as a solvent for measuring solubility.
A: Solubility in CPN is 20% or more B: Solubility in CPN is 10% or more and less than 20% C: Solubility in CPN is 5% or more and less than 10% D: Solubility in CPN is 5% or less

[Dissolution stability]
The dissolution stability of the polymerizable liquid crystal compound synthesized in Examples and Comparative Examples was measured by the method shown below. The results are shown in Tables 3 and 4 below. In the evaluation of the dissolution stability of Examples 1 to 8 in 3 and Table 4 below, the polymerizable liquid crystal compounds described in Tables 3 and 4 below were mixed at the ratios shown in Tables 3 and 4 below. The mixture was evaluated.
Specifically, 1.0 g of the polymerizable liquid crystal compound is weighed in a 10 mL sample bottle in total, and the solvent is added until a predetermined solid content (15% by mass in Table 3 and 30% by mass in Table 4) is reached. , Shake well by hand at 50 ° C., leave at room temperature (23 ° C.) for 10 minutes, and then visually observe.
Then, the sample bottle containing the solution was allowed to pass at 23 ° C. for 28 days. After 14 days and 28 days after preparing the liquid, the presence or absence of precipitation was visually confirmed.
CPN (cyclopentanone) was used as a solvent for measuring dissolution stability.
A: No precipitation was observed and the liquid was clear.
B: No precipitate is observed, but the liquid is slightly turbid.
C: A slight precipitate is observed.
D: A large amount of precipitate is observed.
E: The entire liquid is solidified.

[Examples 1 to 8 and Comparative Examples 1 to 3]
[Manufacturing of optical film]
A polymerizable composition (coating solution for an optically anisotropic film) having the following composition is prepared and coated on a glass substrate with a rubbing-treated polyimide alignment film (SE-150 manufactured by Nissan Chemical Industries, Ltd.) by spin coating. did. The coating film was oriented at 200 ° C. to form a liquid crystal layer. Then, the film was cooled to 135 ° C. and the orientation was fixed by irradiation with ultraviolet rays of 1000 mJ / cm ² , to form an optically anisotropic film, and an optical film for wavelength dispersion measurement was obtained.

―――――――――――――――――――――――――――――――――
Coating liquid for optically anisotropic film ――――――――――――――――――――――――――――――――――
Polymerizable liquid crystal compounds (1) (compounds listed in Table 3 below or Table 4 below)
-Polymerizable liquid crystal compound (2) (Compounds shown in Table 3 below or Table 4 below)
-Photopolymerization initiator (Irgacure 819, manufactured by BASF) 0.45 parts by mass-The following fluorine-containing compound A 0.12 parts by mass-Cyclopentanone 85.00 parts by mass ―――――――――――― ―――――――――――――――――――――
Here, the contents of the polymerizable liquid crystal compounds (1) and (2) were 15 parts by mass in total, and each was blended in the ratios (%) shown in Table 3 and Table 4 below.
In Table 4 below, the mixing ratio of the polymerizable liquid crystal compound (1-1) and (1-3) as the polymerizable liquid crystal compound (1) is 1: 1 and the polymerizable liquid crystal compound (2). ), The mixing ratio of the polymerizable liquid crystal compound (2-1-5) and (2-3-1) is 1: 1.

[Surface]
The surface of the produced optical film was visually confirmed with a polarizing microscope and evaluated according to the following criteria.
A: No bright spots or streaks-like defects B: Some bright spots or streaks-like defects C: Many bright spots or streaks-like defects D: No defects or orientation on the entire surface

From the results shown in Tables 3 and 4 above, it was found that the dissolution stability was inferior when the polymerizable liquid crystal compound (2) was not blended, that is, when the polymerizable liquid crystal compound (1) was used alone (Comparative Examples 1 to 1). 3).
On the other hand, it was found that the mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) had good dissolution stability, and the surface shape of the optical film formed by using the mixture was also good ( Examples 1-8).

Claims (10)

A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by the following formula (1) and a polymerizable liquid crystal compound represented by the following formula (2).
L ^1- SP ^1- D ^3- G ^3- G ^1- D ^1- Ar-D ^2- G ^2- G ^4- D ^4- SP ^2- L ² ... (1)
L ^1- SP ^1- D ^3- A ^3- A ^1- D ^1- Ar-D ^2- A ^2- A ^4- D ^4- SP ^2- L ² ... (2)
In the above formula (1), G ¹ , G ² , G ³ and G ⁴ each independently represent a cyclohexane ring which may have a substituent.
In the above formula (2), A ¹ , A ² , A ³ and A ⁴ are each independently a cyclohexane ring which may have a substituent, or a 6-membered unsaturated ring which may have a substituent. Represents a saturated ring. However, at least one of A ¹ and A ³ represents a 6-membered unsaturated ring which may have a substituent.
In the formulas (1) and (2), D ¹ , D ² , D ³ and D ⁴ are independently single-bonded or -CO-, -O-, -S-, -C (= S). ^{) -, - CR 1 R 2} -, - CR 3 = CR 4 -, - NR 5 -, or a divalent linking group formed from these two or more ^thereof, R 1 to R ⁵ are each Independently, it represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
Further, SP ¹ and SP ² independently have a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of the constituent −CH ₂₋ represents a divalent linking group substituted with −O−, −S−, −NH−, −N (Q) −, or −CO−, where Q represents a divalent linking group. Represents a substituent.
Further, L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, Ar is at least one polymerizable group of the formula If (Ar-3) an aromatic ring represented by the, ^{L 1} and ^{L 2} and ^{L 3} and ^{L 4} in formula (Ar-3) Represents.
Further, Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5).
Here, in the formulas (Ar-1) to (Ar-5), * represents a bonding position with D ¹ or D ² .
Further, Q ¹ represents N or CH.
Further, Q ² represents -S-, -O-, or -N (R ⁶ )-, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Further, Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent.
In addition, Z ¹ , Z ² and Z ³ independently have a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. It represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ⁷ , -NR ⁸ R ⁹ , or -SR ¹⁰ , and R ^{7 to} R ¹⁰ are each. Independently, they represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring.
Further, A ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N (R ¹¹ )-, -S-, and -CO-, and R ¹¹ is hydrogen. Represents an atom or substituent.
Further, X represents a non-metal atom of Group 14 to 16 to which a hydrogen atom or a substituent may be bonded.
In addition, D ⁵ and D ⁶ are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR ¹ R ^2- , -CR ³ = CR, respectively. ^It represents a divalent linking group consisting of 4-, -NR ^5- , or a combination of two or more of these, and R ^{1 to} R ⁵ independently represent a hydrogen atom, a fluorine atom, or 1 to 1 carbon atoms. Represents an alkyl group of 4.
Further, SP ³ and SP ⁴ independently have a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of the constituent −CH ₂₋ represents a divalent linking group substituted with −O−, −S−, −NH−, −N (Q) −, or −CO−, where Q represents a divalent linking group. Represents a substituent.
Further, L ³ and L ⁴ independently represent monovalent organic groups, respectively, and at least one of L ³ and L ⁴ and L ¹ and L ^{2 in} the above formula (1) or (2) has a polymerizable group. Represent.
In addition, Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle.
Further, Ay is an alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom and a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. Represents an organic group having 2 to 30 carbon atoms.
Further, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, Q ³ represents a hydrogen atom or may have a substituent alkyl group having 1 to 6 carbon atoms. The polymerizable liquid crystal according to claim 1, wherein D ¹ and D ^{2 in the} formulas (1) and (2) are both −CO—O− *, and * represents a bonding position with Ar. Composition. Formula (1) and (2) ^{D 3} and ^{D 4} in the are both a -CO-O- *, * represents a bonding position to SP ¹ or SP ^2, claim 1 or 2 The polymerizable liquid crystal composition according to. The polymerizable liquid crystal composition according to any one of claims 1 to 3, wherein both L ¹ and L ^{2 in the} formulas (1) and (2) represent a polymerizable group. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein A ¹ and A ³ in the formula (2) represent a cyclohexane ring and the other represents a benzene ring. The polymerizable liquid crystal composition according to any one of claims 1 to 5, wherein both A ² and A ⁴ in the formula (2) represent a cyclohexane ring. An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 6. An optical film having the optically anisotropic film according to claim 7. A polarizing plate having the optical film according to claim 8 and a polarizer. An image display device having the optical film according to claim 8 or the polarizing plate according to claim 9.